Cyclohexylamine condensation products



Patented Dec. 15,1931

, xmmnmss mnannivnenn n EICKE, F FRA KrORT-oN-TnEMAImHoonsT, [GERQ MANY, ASSIGNO BSVTO GENERAL ANILINE WORKS, INC, OF NEW YORK, N. Y A COR- romi'rroiv or DELAWARE mmaexmmmecomment-101w PRODUCTS No Drawing. Application flle d October 11, 1929', ser1a1 n..399,087, and in German marches; 192s.

, 7 general formula:

'10 wherein one represents N0 l lI I thei The present'invention relates to new condensation products. Moreparticularly, it relates to the new compounds of the following other X being hydrogen, halogen, a'sulfonic or'a carboxylic acid group. The compounds of the'above given general formulagare obtainable, for instancaby condensing any cyclohexylamine, viz. 'a' compound of the constitution of the cyclohe'xylamine, whose hydrogen atoms linked t-oa C-atom maybe substituted or not, such asg -for instance,.cyclohexylaming 'metyl cyclohexylamine or the like, with acompound of the 'following generalformula: V U

' v 1 I V X1 a wherein Y represents an exchangeable halogen atom, one, X being N0 the other X being hydrogen, halogen, a sulfonic or a carboxylic acid group, andreducing, if desired, the nitro compound s, thus obtained, to the corresponding amino compounds.

The condensation ispreferably'conducted V in the presence'of an acid binding agent and a carrier such as, for instance; copperpowder or a copper salt. In some cases the; reaction can be acceleratedby working in -a' pressure vessel.

Part of our new compounds are dyestufi Fs.

- All of'them are valuable starting materials for the preparation ,lof' other 1 new products and dyestufis. The condensation product from cycloherkylamine;,and l-chloro-t-nitrobenzeneQ-sulfonic acid, forfinstance, yields, after being reduced, a-productfrom which,

V for. instance, by nfurther condensation, with 1 chloroQ 4;din'itrobenzene or with ol -chloro- 'dinitronaphthalene, acid wool dyestuflfs can be obtained. From the. nitrophenyLcyclohexylamine sulfonic acids obtainable-accord- ;In concentrated sulfuric acid the limit itthereto, the parts being by weight unless otherwise stated.

1. 19.8 parts otcyclohexylamine are heated in a reflux apparatus for about 3 hours with 20 parts ofl-chloro'-2.4-dinitro benzene in 200 parts-by volumeofalcohol. The condensationproduct separates in the form ofyellow crystals; It is insoluble in water and can be obtained from alcohol 'in the'form'of yellow lamellee'of the melting point 154 C. It is readily soluble in benzene and acetone, s'paringly'soluble in alcohol;

lna similar manner the l-N cyclohexylamino4-chloro 2 nitrobenzene of the melt- 7 ing point 104? Ciis obtained from the 1.4 dichloro-2-nitrobenz'ene by heating 'it in an autoclave with'cyclohexylamine. 2; By replacing in Example 1 the 1"- chloro-- 2-.4g-dinitro-benzene by the equivalent quantity 1 of 1-chloro-24-dinitro-naphthalene,' ayel lowish-red condensation product is obtained which isverysparingly soluble in alcohol. I

new productprecipitates in the form of yellow crystals; .The portion which remains in solutioncan be obtained salting it out:

- ",When recrystallizing the product from watergreenish-yellowcrystals are obtained 7 which dye wool and acetate silk yellow tints. product dissolves to acolorless solution. 1

-- l-.I-10,; parts of cyclohexylamine are-dissolved together with 32 parts of potassium 1- chloro-2.6-dinitro-benzeneA sulfonate with addition, of 6 parts of calcined sodium carbonate in 200 parts of water and boiled 1n a reflux apparatus for about 8 hours. A redidish-yellow powder is obtained which, when 71 redissolved in hot water,crystall1zes out 1n 3. 10 parts of cyclohexylamine are disthe form of reddish-yellow laminae. In cold sulfuric acid the product dissolves to a colorless solution, which when heated turns yellow. It dyes wool in an acid solution yellow tints.

5. 100 parts of the condensation product obtainable according to Example 3. from cyclohexylamine and l-chloro-l-nitrobenzene-2-sodium sulfonate are dissolved in about 1000 parts-of waterand reducedinneutra-l solution in the usual manner at about 70 C. to 80 C. with previously cauterized iron. The reduction mass rendered alkaline by the addition of sodium carbonate is filtered by suction and .the solution is neutralized by means of hydrochloric acid. 'The 1-N-cyc1ohexylamino- L -nitrobenzene 2 -sulif'oni0 acid thus obtained precipitates in the form of .a white sandy powder. It dissolvessparingly in water but readily in alkalics and warnrdiluteh-ydrochloric acid. Vhenadding ferric chloride to its aqueous solution, it first assumesareddish-violetcoloration which after some time turns blue.

6.. parts of cyclohexylamine are dissolved together with 26 parts of .l-chlorolnitrobenzene-2-sodium sulfonate-with'the addition'o 'f 6 ,partsiof calcined sodium carbonate and 0.2 part oicopper powder in 250 parts of'water and the solution 'is'boiled in a reflux apparatus ioinabout 7 to 8 hours. The prod- :uct obtained is identical with thatdescri-bed in Example 3.

7. 10 parts of cyclohexylamine are dissolved together with .26 parts of I-chloroA- nitrobenzene-2-sodi1un sultonate with the ad- .(lition of 6 parts of calcined sodium carbomate inz300 parts ofwater. T-he solution "is heated in a pressure vessel iorahout 6 hours up to .a temperature of about 135 C. to 140 C. The resulting product is identical with that obtained according to Example 3. The l-N-cyc-lohexylaminefnitrobenzene- 2-carboxylic acid melting .at about 253 C. with decomposition can be obtained in an analogous manner by condensing cycloheX- yl'amine with 1-chloroi-nitrobenzene-2-car' boxylic acid.

.8. 10 parts of hexahydroaniline are boiled 'inia reflux apparatus 'for abouttO hours with about 200 partsof watcr,;23.8 parts of l-chlo- -ro-2-nitrobenzene--sulfonic acid and 12 parts of sodium carbonate and the solution thus obtained is filtered while hot so as to eliminate small quantities oi impurities. 'Oncooling the 1-N-cyclohexylamino-2 nitro-benzenei-sodium sulton ate precipitates from the filtrate in the form ofgol'den-yellow crystals.

The condensation product dyes wool and silk very even brilliant yellow tints.

Other condensation products such as, for

i instance, 1 -N-c y.clohexylamino 2.4- dinitro- In a'similar manner the l-N-cyclohexylam lIlO-lQ-JllllJIOl'JBllZBIlB of the melting point 104 C. can beobtained from the l-N-cyclohexylamino-2-nitrobenzenebsulfonic :acid obtainable by condensing cyclohexylamine with 1- chloro-2-nitrobenzene-4-sulfonic acid and the 1-N-cyclohexylamino-2.4-dinitrobenzene of the melting point 15at "C. from the l-N-cyclohexylaminoa-24 dinitrobenzene 6 sulfonic acid obtainable by condensing cyclohexyl- .aniinewith l-chloro-2Ac-dinitrobenzene-6-sul- -tonic acid.

Instead of-su'lfuric-acid, hydrochloric acid or other water-containing mineral acids may be used in order to splitofi the sulfo group. Also the concentration of the acids and the Q5 temperature may vary within wide limits.

By :reducingthe nitro derivatives described in the present specification according to known methods the =correspon'ding -aminoaryl-eyclohe'xylamines are obtained. I

We claim: 7

1. As new products, the compounds of the following general formula:

wherein one .X stands for a NO or NI-I group, the other X for a sulfo group, being when containing a N0 group yellow, otherwise colorlessproducts which are soluble in alkalies.

2. As new'products, the compounds of the following general formula:

SOgONH.

yellow, otherwise colorless products which are .solublein alkalies.

3. As a new product, the compound of the following formula:

HI SOzONa y l E f 8 H v N H 11: NH:

8' V a v being a white powder which is sparingly soluble in water, readily soluble in alkalies and dilute hydrochloric acid and the aqueous solution of which readily turns'blue on addition of iron chloride. V

4. As new products, the compounds of the following general formula:

cyclohexyl-NH wherein one X represents N0 or NH the other X being hydrogen, ch1orine,-a sulfonic or a carboxylic acid group and wherein the cyclohexyl residue may be substituted by methyl.

5. As new products, the compounds of the following general formula: f

wherein one X re resents N0 or N H the other X being by rogen, chlorine, a sulfonio or a carboxylic acid group. I

In testimony whereof, we aflix our signatures.

KARL THIESS. BERNHARD DEIOKE. 

